P
US9206154B2ActiveUtilityPatentIndex 39

Inverse agonists and neutral antagonists for the TSH receptor

Assignee: GERSHENGORN MARVINPriority: Apr 8, 2010Filed: Apr 8, 2011Granted: Dec 8, 2015
Est. expiryApr 8, 2030(~3.8 yrs left)· nominal 20-yr term from priority
Inventors:GERSHENGORN MARVINNEUMANN SUSANNEHUANG WENWEITHOMAS CRAIG J
A61P 43/00A61P 35/04A61P 35/00A61P 5/14C07D 405/06A61K 31/517C07D 401/06C07D 239/91A61P 27/02
39
PatentIndex Score
0
Cited by
53
References
61
Claims

Abstract

TSHR inverse agonists and neutral antagonists that are useful for treating Graves' orbitopathy, Graves' hyperthyroidism and/or thyroid cancer.

Claims

exact text as granted — not AI-modified
What is claimed is:  
     
       1. A compound, or a pharmaceutically acceptable salt or ester thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl; 
         R 2  is H, alkoxy, alkyl, substituted alkyl or halogen; and 
         R 3 -R 7  are each individually selected from H, alkyl, substituted alkyl, or aminocarbonyl, provided that at least one of R 3  or R 7  is not H; and 
         X is O or S; provided that the compound is not 
       
       
         
           
           
               
               
           
         
       
     
     
       2. The compound of  claim 1 , wherein R 1  is selected from furan-2-ylmethyl, pyridin-3-ylmethyl, thien-2-ylmethyl or methoxyethyl. 
     
     
       3. The compound of  claim 1 , wherein R 2  is methoxy. 
     
     
       4. The compound of  claim 1 , wherein R 3  and R 7  are each methyl. 
     
     
       5. The compound of  claim 1 , wherein X is O. 
     
     
       6. The compound of  claim 1 , wherein X is S. 
     
     
       7. The compound of  claim 1 , wherein R 5  is an aminocarbonyl group. 
     
     
       8. The compound of  claim 1 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       9. The compound of  claim 1 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       10. The compound of  claim 1 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       11. The compound of  claim 1 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       12. The compound of  claim 1 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       13. A compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl; 
         R 2  is H, alkoxy, alkyl, substituted alkyl or halogen; 
         R 3  and R 7  are each individually alkyl; 
         R 4 -R 6  are each individually selected from H, alkyl, substituted alkyl, halogen, or aminocarbonyl; and 
         X is O or S; provided that the compound is not 
       
       
         
           
           
               
               
           
         
       
     
     
       14. The compound of  claim 13 , wherein R 3  and R 7  are each methyl. 
     
     
       15. A compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl; 
         R 2  is H, alkoxy, alkyl, substituted alkyl or halogen; 
         R 3 , R 4 , R 6  and R 7  are each individually selected from H, alkyl, substituted alkyl, halogen, or aminocarbonyl, provided that at least one of R 3  or R 7  is not H; 
         R 5  is aminocarbonyl; and 
         X is O or S. 
       
     
     
       16. The compound of  claim 2 , wherein R 3  and R 7  are each methyl. 
     
     
       17. The compound of  claim 15 , wherein R 5  is acetamido. 
     
     
       18. A pharmaceutical composition comprising at least one pharmaceutically acceptable additive and a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl; 
         R 2  is H, alkoxy, alkyl, substituted alkyl or halogen; and 
         R 3 -R 7  are each individually selected from H, alkyl, substituted alkyl, halogen, or aminocarbonyl, provided that at least one of R 3  or R 7  is not H; and 
         X is O or S. 
       
     
     
       19. The pharmaceutical composition of  claim 18 , wherein R 1  is selected is selected from furan-2-ylmethyl, pyridin-3-ylmethyl, thien-2-ylmethyl or methoxyethyl. 
     
     
       20. The pharmaceutical composition of  claim 18 , R 3  and R 7  are each methyl. 
     
     
       21. A pharmaceutical composition comprising at least one pharmaceutically acceptable additive and a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt or ester thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from: 
       
       
         
           
           
               
               
           
         
       
       and
 R 2 -R 6  are each individually selected from H, alkyl, substituted alkyl or halogen. 
 
     
     
       22. The pharmaceutical composition of  claim 21 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       23. The pharmaceutical composition of  claim 21 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       24. A method of treating Graves' disease in a subject, comprising administering to the subject an inverse agonist of TSHR or a neutral antagonist of TSHR. 
     
     
       25. The method of  claim 24 , wherein the inverse agonist of TSHR or the neutral antagonist of TSHR comprises a 2,3-dihydroquinazolin-4-one compound. 
     
     
       26. A method of treating Graves' disease in a subject, comprising administering to the subject a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl; 
         R 2  is H, alkoxy, alkyl, substituted alkyl or halogen; and 
         R 3 -R 7  are each individually selected from H, alkyl, substituted alkyl, halogen, or aminocarbonyl; and 
         X is O or S. 
       
     
     
       27. The method of  claim 24 , wherein the Graves' disease is Graves' orbitopathy. 
     
     
       28. The method of  claim 24 , wherein the Graves' disease is Graves' hyperthyroidism. 
     
     
       29. The method of  claim 28 , wherein the Graves' hyperthyroidism is recurrent Graves' hyperthyroidism following radioiodine or anti-thyroid treatment. 
     
     
       30. A method for inhibiting signaling stimulated by thyroid-stimulating antibodies (TSAbs) in a subject, comprising administering to the subject a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl; 
         R 2  is H, alkoxy, alkyl, substituted alkyl or halogen; and 
         R 3 -R 7  are each individually selected from H, alkyl, substituted alkyl, halogen, or aminocarbonyl; and 
         X is O or S. 
       
     
     
       31. The method of  claim 30 , wherein the method comprises inhibiting stimulation of the thyroid-stimulating hormone receptor by TSAbs in thyroid or retro-orbital cells. 
     
     
       32. A method of treating hyperthyroidism in a subject, comprising administering to the subject a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl; 
         R 2  is H, alkoxy, alkyl, substituted alkyl or halogen; and 
         R 3 -R 7  are each individually selected from H, alkyl, substituted alkyl, halogen, or aminocarbonyl; and 
         X is O or S. 
       
     
     
       33. A method of treating thyroid cancer in a subject, comprising administering to the subject a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl; 
         R 2  is H, alkoxy, alkyl, substituted alkyl or halogen; and 
         R 3 -R 7  are each individually selected from H, alkyl, substituted alkyl, halogen, or aminocarbonyl, provided that at least one of R 3  or R 7  is not H; and 
         X is O or S. 
       
     
     
       34. The method of  claim 33 , wherein the method comprises administering the compound subsequent to thyroid cancer surgery or radioactive iodine therapy. 
     
     
       35. The method of  claim 33 , further comprising co-administering thyroid hormone therapy to the subject. 
     
     
       36. The method of  claim 33 , wherein the thyroid cancer is recurrent or metastatic thyroid cancer. 
     
     
       37. The method of  claim 33 , wherein administration of thyroid hormone is contraindicated in the subject. 
     
     
       38. The method of  claim 36 , wherein the thyroid cancer is recurrent despite suppression of the subject's endogenous thyroid-stimulating hormone. 
     
     
       39. The method of  claim 36 , wherein the thyroid cancer exhibits basal TSHR signaling activity and the compound inhibits such activity. 
     
     
       40. The method of  claim 26 , wherein R 1  is selected from furan-2-ylmethyl, pyridin-3-ylmethyl, thien-2-ylmethyl or methoxyethyl. 
     
     
       41. The method of  claim 26 , wherein R 2  is methoxy. 
     
     
       42. The method of  claim 26 , wherein R 3  and R 7  are each methyl. 
     
     
       43. The method of  claim 26 , wherein X is O. 
     
     
       44. The method of  claim 26 , wherein X is S. 
     
     
       45. The method of  claim 26 , R 5  is an aminocarbonyl group. 
     
     
       46. The method of  claim 26 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       47. The method of  claim 26 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       48. The method of  claim 16 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       49. The method of  claim 26 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       50. The method of  claim 26 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       51. The method of  claim 26 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       52. A method of treating thyroid cancer in a subject, comprising administering to the subject a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from: 
       
       
         
           
           
               
               
           
         
       
       and
 R 2 -R 6  are each individually selected from H, alkyl, substituted alkyl or halogen. 
 
     
     
       53. The method of  claim 52 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       54. The method of  claim 52 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       55. A method of treating hyperthyroidism in a subject, comprising administering to the subject a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from: 
       
       
         
           
           
               
               
           
         
       
       and
 R 2 -R 6  are each individually selected from H, alkyl, substituted alkyl or halogen. 
 
     
     
       56. The method of  claim 55 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       57. The method of  claim 55 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       58. A method of treating Graves' disease in a subject, comprising administering to the subject a therapeutically effective amount of at least one compound, or a pharmaceutically acceptable salt or ester thereof, having a structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from: 
       
       
         
           
           
               
               
           
         
       
       and
 R 2 -R 6  are each individually selected from H, alkyl, substituted alkyl or halogen. 
 
     
     
       59. The method of  claim 27 , wherein the compound is: 
       
         
           
           
               
               
           
         
       
     
     
       60. The method of  claim 27 , wherein R 1  is selected from furan-2-ylmethyl or pyridin-3-ylmethyl; R 2  is methoxy; and R 3  and R 7  are each methyl. 
     
     
       61. The method of  claim 25 , wherein the 2,3-dihydroquinazolin-4-one compound is a 2-substituted, 3-substituted 2,3-dihydroquinazolin-4-one compound, wherein the substituent at the 2-position is a furanyl-containing group, a pyridinyl-containing group, a thienyl-containing group, hydroxyalkyl, or alkoxyalkyl, and the substituent at the 3-position is —Ar 1 —CH 2 —X—Ar 2 , wherein Ar 1  is a substituted or unsubstituted arylene group; Ar 2  is a substituted or unsubstituted aryl group; and X is O or S.

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